JP2020185700A - Manufacturing method of flow path device - Google Patents

Abstract

To provide a method capable of manufacturing a flow path device capable of maintaining a hydrophilicity of a flow path surface for a long period of time, in a method of manufacturing the flow path device having a flow path for flowing a liquid inside by crimping two or more members.SOLUTION: In at least one of two or more members constituting a flow path device, a process liquid containing a hydrophilic agent is used to form a hydrophilic coating that covers a surface of the member to be joined to the other members, and then in the member provided with the hydrophilic coating, plasma derived from ultraviolet rays or oxygen-containing gas is applied only to a joint surface of the hydrophilic coating, and for members that do not have a hydrophilic coating, at least the joint surface is irradiated with plasma derived from ultraviolet rays or oxygen-containing gas, and two or more members that have undergone such treatment are crimped to manufacture the flow path device.SELECTED DRAWING: Figure 1

Description

The present invention relates to a method for manufacturing a flow path device including a flow path for flowing a liquid inside.

In recent years, in the field of biochemical analysis and the like, a flow path having a flow path for flowing a liquid inside, such as a micro flow path chip having a fine flow path for the purpose of performing precise analysis using a small amount of sample, etc. The use of devices is widespread. A liquid sample containing water is often flowed through such a flow path device. Therefore, in order to allow the sample to flow smoothly through the fine flow path, a high degree of hydrophilicity is desired on the surface of the flow path of the flow path device.

As a method for manufacturing a channel device having a hydrophilic surface of the channel, for example, a part of the channel device made of a resin such as polymethylmethacrylate, cycloolefin polymer, and polyetheretherketone is irradiated with vacuum ultraviolet rays. A method is known in which a flow path device is manufactured by crimping parts irradiated with vacuum ultraviolet rays after hydrophilizing and activating the surface of the parts. (Patent Document 1)

Japanese Patent No. 4993243

However, in the method of crimping parts irradiated with vacuum ultraviolet rays as described in Patent Document 1, there is a problem that the hydrophilicity of the flow path surface tends to decrease with time even if there is no problem in crimping the parts. There is.

The present invention has been made in view of the above problems, and is a method for manufacturing a flow path device provided with a flow path for crimping two or more members to allow a liquid to flow inside, and is a method for manufacturing a flow path device for a long period of time. It is an object of the present invention to provide a method capable of manufacturing a flow path device capable of maintaining the hydrophilicity of a surface.

The present inventors form a hydrophilic film using a treatment liquid containing a hydrophilic agent on at least one of two or more members constituting the flow path device, and then, in the member provided with the hydrophilic film, hydrophilicity. The above problem can be solved by irradiating the joint surface (joint portion) of the chemical coating with plasma derived from ultraviolet rays or oxygen-containing gas and then crimping two or more members to manufacture a flow path device. The present invention has been completed.

Specifically, the present invention is a method for manufacturing a flow path device including a flow path for flowing a liquid inside.
Two or more members are prepared as members constituting the flow path device, and at least one of the members is made hydrophilic by using a treatment liquid containing a hydrophilic agent to coat the surface of the member on the side to be joined with the other members. The film forming process and the film forming process to form a chemical film,
In the member provided with the hydrophilic film, only the joint surface of the hydrophilic film is selectively irradiated with plasma derived from ultraviolet rays or oxygen-containing gas, and for the member not provided with the hydrophilic film, at least the joint surface is irradiated. In contrast to the irradiation step of irradiating plasma derived from ultraviolet rays or oxygen-containing gas,
An external force is applied to the two or more members arranged at predetermined positions so that the joint surfaces of the two or more members treated with ultraviolet rays or the plasma face each other, and the joint surfaces are crimped to each other. Crimping process and
It is a manufacturing method including.

According to the present invention, there is a method for manufacturing a flow path device including a flow path in which two or more members are crimped to allow a liquid to flow inside, and a flow path device capable of maintaining hydrophilicity on the surface of the flow path for a long period of time. Can be provided with a method capable of manufacturing.

It is a figure which shows typically one preferable embodiment of this invention.

≪Manufacturing method of flow path device≫
A method for manufacturing a flow path device having a flow path for flowing a liquid inside is
Two or more members are prepared as members constituting the flow path device, and at least one of the members is made hydrophilic by using a treatment liquid containing a hydrophilic agent to coat the surface of the member on the side to be joined with the other members. The film forming process and the film forming process to form a chemical film,
In the member provided with the hydrophilic film, only the joint surface of the hydrophilic film is selectively irradiated with plasma derived from ultraviolet rays or oxygen-containing gas, and for the member not provided with the hydrophilic film, at least the joint surface is irradiated. In contrast to the irradiation step of irradiating plasma derived from ultraviolet rays or oxygen-containing gas,
An external force is applied to the two or more members arranged at predetermined positions so that the joint surfaces of the two or more members treated with ultraviolet rays or the plasma face each other, and the joint surfaces are crimped to each other. Crimping process and
including.

The shape of the flow path device is not particularly limited. Examples of the shape of the flow path device include a plate shape, a disk shape, a columnar shape, a triangular columnar shape, a triangular columnar shape, a prismatic shape such as a hexagonal columnar shape, and the like.

The flow path included in the flow path device may be linear without branching, or may be branched with one or more branching points. The flow path device may include only one flow path, or may include a plurality of flow paths of two or more.

The cross-sectional shape of the flow path is not particularly limited. For example, from the viewpoint that the flow path can be easily formed by a photolithography method, an imprint method, or the like, the cross-sectional shape of the flow path is preferably a quadrangle such as a square or a rectangle. On the other hand, the cross-sectional shape of the flow path is circular or substantially circular because it is easy for the fluid to flow smoothly and when the fluid flowing in the flow path contains solid content, the solid content is unlikely to accumulate in the flow path. It is preferable to have it.

The cross-sectional area of the flow path is not particularly limited, and is appropriately set according to the application of the flow path device. The cross-sectional area of the flow path may or may not be constant within the flow path device.
Further, the size of the cross section of the flow path is not particularly limited. As for the size of the cross section of the flow path, the length of the minor axis in the ferret system is preferably 1 mm or less, more preferably 500 μm or less, even more preferably 100 μm or less, and particularly preferably 50 μm or less. The lower limit of the length of the minor axis in the Ferret system is not particularly limited, and may be, for example, 1 μm or more, 5 μm or more, or 10 μm or more.
The ferret diameter is the length of the side of the rectangle or square having the smallest area among the rectangles or squares circumscribing the outer circumference of the cross section of the flow path. When the cross-sectional shape is a circle, it is the value of the diameter of the circle, and when the cross-sectional shape is a square, it is the length of one side of the square.

For example, consider a linear cross section in which a rectangle having a width of 10 μm and a length of 50 μm is bent at a position where the length from the end is 25 μm so that both ends overlap. In this case, the ferret diameter is approximately 20 μm (= width 10 μm + width 10 μm) and 25 μm (= length 50 μm ÷ 2). Therefore, the minor axis of the ferret diameter is about 20 μm.
Therefore, in this case, 20 μm is adopted as the minor diameter of the ferret diameter.

Each step will be described below.

<Film formation process>
In the film forming step, two or more members are prepared as members constituting the flow path device, and at least one of the members is on the side to be joined to the other members of the member by using a treatment liquid containing a hydrophilic agent. A hydrophilic film is formed to cover the surface.

In the above manufacturing method, the surface of the surface to which two or more members are joined is activated by irradiation with plasma derived from ultraviolet rays or oxygen-containing gas, and then the two or more members are crimped to form a flow path device. Manufactured.

The material of the member is not particularly limited as long as it is a material that can be crimped by activation by irradiation with plasma derived from ultraviolet rays or oxygen-containing gas. The member material may be an inorganic material or an organic material typified by a resin.
Regarding the members, the surface material on the side to be joined to each other member is silicon, glass, silicone resin, or annular because of the ease of adhesion of the hydrophilic coating and the ease of activation by irradiation with ultraviolet rays or plasma. One or more selected from the group consisting of olefin polymers, cyclic olefin copolymers, acrylic resins, polyester resins, and polycarbonate resins is preferable.

In the above manufacturing method, at least two of the two or more members usually include surfaces that form a flow path. Then, a hydrophilic film is formed on the surface forming the flow path.
Since the purpose is to manufacture a channel device having a hydrophilic surface, in this case, the portion of the hydrophilic film that is not irradiated with plasma derived from ultraviolet rays or oxygen-containing gas is the flow of the channel device. It becomes the road surface. This is because at least a part or all of the hydrophilic film is removed at the place where the hydrophilic film is irradiated with ultraviolet rays or plasma derived from an oxygen-containing gas.

Further, it is preferable that a hydrophilic film is formed on all of the two or more members constituting the flow path device. By forming a hydrophilic coating on all of the two or more members constituting the flow path device, the entire inner surface of the flow path is satisfactorily hydrophilized.

In the film forming step, depending on the material of the member, before forming the hydrophilic film, plasma derived from ultraviolet rays or oxygen-containing gas is applied to the surface of the member constituting the flow path device on which the hydrophilic film is formed. Or a treatment of contacting with an oxidizing agent may be performed. By forming a hydrophilic film after such treatment, the hydrophilic film can be firmly adhered to the surface of the member.

When an oxidizing agent is used in the above treatment performed before the film forming step, the oxidizing agent is preferably at least one selected from the group consisting of sulfuric acid, nitric acid, chromic acid, permanganate, persulfuric acid, and mixed acid. ..

The hydrophilizing agent may be an organic compound or an inorganic compound. When the surface on which the hydrophilic film is formed is irradiated with ultraviolet rays or plasma derived from an oxygen-containing gas, the surface irradiated with ultraviolet rays or plasma can be easily crimped, so that the hydrophilic agent is an organic compound. Is preferable. This is because when the hydrophilic film is mainly composed of an organic compound, the removal of the hydrophilic film and the activity of the surface of the member by irradiation with ultraviolet rays or plasma are likely to proceed satisfactorily at the same time by irradiation with ultraviolet rays or plasma.

The method of applying the treatment liquid to the surface of the member is not particularly limited. Specific examples of the coating method include a spin coating method, a spray method, a roller coating method, a dipping method and the like. When the member is plate-shaped, the spin coating method is preferable as the coating method because it is easy to uniformly apply the treatment liquid.

For the purpose of thinning the hydrophilized film, the coating film formed by applying the treatment liquid may be rinsed. The rinsing solution is not particularly limited as long as a film having a desired film thickness can be formed. As the rinsing solution, water, an organic solvent, and an aqueous solution of an organic solvent can be used. Water is preferable as the rinsing solution.
The method for rinsing the coating film is not particularly limited. Typically, the coating film is rinsed by bringing the rinsing solution into contact with the coating film by the same method as the above-mentioned coating method.

The film thickness of the hydrophilized coating is not particularly limited as long as it does not impair the object of the present invention. The film thickness of the hydrophilized coating is, for example, preferably 100 nm or less, more preferably 10 nm or less, and preferably 0.1 nm or more. The lower limit of the film thickness of the hydrophilized coating is more preferably 0.5 nm or more. Within the above film thickness range, 0.5 nm or more and 5 nm or less is particularly preferable, and 0.5 nm or more and 3 nm or less is most preferable.

When the thickness of the hydrophilic coating 12 is within the above range, it is easy to obtain a sufficient hydrophilic effect, and the surface on which the hydrophilic coating 12 is formed is irradiated with ultraviolet rays or plasma derived from an oxygen-containing gas. When this is done, it is easy to crimp the surface irradiated with ultraviolet rays or plasma.
The thickness of the hydrophilized coating film 12 is adjusted by adjusting the solid content concentration of the treatment liquid, the film thickness of the coating film when applying the treatment liquid, the amount of the rinse liquid used, the type of the rinse liquid, the temperature of the rinse liquid, and the like. It can be adjusted by.

The treatment liquid used for forming the hydrophilic film is not particularly limited as long as it can form a film that hydrophilizes the surface of the member.

As the treatment liquid used for forming the hydrophilic film, a solution of a resin having a hydrophilic group is preferably used. The solvent contained in the treatment liquid is not particularly limited as long as the resin is dissolved. Preferred solvents include the solvent described for (B) solvent contained in the first treatment liquid described later.
The concentration of the resin in the treatment liquid containing the resin having a hydrophilic machine is not particularly limited. The concentration of the resin in the treatment liquid is appropriately determined in consideration of the film thickness of the hydrophilized coating and the coatability of the treatment liquid.
The resin having a hydrophilic group is not particularly limited. Examples of the resin having a hydrophilic group include (meth) acrylic resin, novolak resin, polyester resin, polyamide resin, polyimide resin, polyamideimide resin, polyalkyleneimine resin (for example, polyethyleneimine resin), and silicone resin. Can be mentioned. Among these resins, (meth) acrylic resin is preferable because it is easy to introduce a functional group and adjust the content ratio of a unit having a functional group.
Specific examples of the hydrophilic group include a polyoxyalkylene group (for example, a polyoxyethylene group, a polyoxypropylene group, a polyoxyalkylene group in which an oxyethylene group and an oxypropylene group are blocked or randomly bonded), an amino group, and a carboxy group. Examples include groups, hydroxyl groups, sulfonic acid groups and the like. Further, an organic group containing these groups is also preferable as a hydrophilic group.
Further, a cationic group composed of an anion portion and a cation portion bonded to the resin is also preferable as the hydrophilic group. Examples of the cation portion constituting the cationic group include a nitrogen-containing cation portion, a sulfur-containing cation portion, an iodine-containing cation portion, and a phosphorus-containing cation portion. The anion constituting the anion portion is not particularly limited. The valence of the anion is not particularly limited, and a monovalent anion or a divalent anion is preferable, and a monovalent anion is more preferable.
Preferable examples of the monovalent anion as the anion portion include halide ions, hydroxide ions, nitrate ions, organic acid ions derived from various organic carboxylic acids and organic sulfonic acids, and the like. Among these, halide ions are preferable, chloride ions, bromide ions, iodide ions, and fluoride ions are more preferable, chloride ions and bromide ions are even more preferable, and chloride ions are particularly preferable.
Preferred examples of the cationic group include a group containing a quaternary ammonium base, a group containing a salt of a nitrogen-containing aromatic heterocyclic group, a group containing a sulfonium base, a group containing an iodonium base, a group containing a phosphonium base and the like. Be done.
Among these cationic groups, a group containing a quaternary ammonium base is preferable because it can be easily introduced into a resin and has a high hydrophilicity effect.
Further, for the purpose of imparting adhesion to the member and durability to peeling to the hydrophilic film, the resin contains an epoxy group-containing group such as a glycidyl group, an oxetanyl group-containing group, a trimethoxysilyl group and a triethoxysilyl group. It may have a hydrolysis-condensable reactive silyl group such as a group.

As an example of a preferable treatment liquid used for forming a hydrophilized film, there is a treatment liquid described in JP-A-2018-159039.
The treatment liquid described in JP-A-2018-159039 contains a resin and a solvent. The resin has a functional group I, which is one or more groups selected from the group consisting of a hydroxyl group, a cyano group, and a carboxy group, and a functional group II, which is a hydrophilic group other than the functional group I. When the functional group II contains one or more groups selected from a hydroxyl group, a cyano group, and a carboxy group, the resin does not have to have the functional group I. In the treatment liquid described in JP-A-2018-159039, the weight average molecular weight of the resin is 100,000 or more.

The treatment liquid described in JP-A-2018-095756 can also be suitably used for forming a hydrophilized film.
The treatment liquid described in JP-A-2018-095756 contains a resin, an ionic compound, and a water-containing solvent. The resin is a water-soluble resin having an anionic group and / or a cationic group. The ionic compound is a water-soluble non-polymer compound.

A two-component treatment solution composed of a first solution and a second solution described in JP-A-2018-094516 can also be suitably used for forming a hydrophilic film.
Regarding the treatment liquid described in JP-A-2018-094516, the first liquid contains a resin and a water-containing solvent. The resin contained in the first liquid is a water-soluble resin having an anionic group and / or a cationic group.
The second liquid contains an ionic compound and a water-containing solvent. The ionic compound contained in the second liquid is a water-soluble non-polymer compound.
In the case of forming a hydrophilized film using a two-component treatment solution composed of a first solution and a second solution described in JP-A-2018-094516, the first solution is applied after the first solution is applied. The second liquid is brought into contact with the place where the liquid is applied.

The treatment liquid described in JP-A-2017-061682 can also be suitably used for forming a hydrophilized film.
The treatment liquid described in JP-A-2017-061682 contains a resin, a strong acid, and a solvent. The resin has a functional group I, which is one or more groups selected from the group consisting of a hydroxyl group, a cyano group, and a carboxy group, and a functional group II, which is a hydrophilic group other than the functional group I. However, when the functional group II contains one or more groups selected from the group consisting of a hydroxyl group, a cyano group, and a carboxy group, the resin does not have to have the above-mentioned functional group I. The pKa of the strong acid contained in the treatment liquid described in JP-A-2017-061682 is 1 or less.

Specific examples of a particularly preferable treatment liquid include (A) resin and (B) solvent.
(A) The ratio of structural units having anionic groups to all structural units of the resin is 5 mol% or less.
The resin (A) has a functional group I which is a hydroxyl group and / or a cyano group and a functional group II which is a hydrophilic group other than the functional group I, except that the functional group II is a hydroxyl group and / or cyano. When containing a group, the resin (A) does not have to have a functional group I, and examples thereof include a treatment liquid.
This treatment liquid will be described as a "first treatment liquid".

The first treatment liquid can be used for surface treatment of various base materials. The first treatment liquid is particularly preferably used for forming a hydrophilized film on a member containing polyorganosiloxane in at least a part of the surface. When the first treatment liquid satisfying the above-mentioned predetermined requirements is used, it is easy to make the base material containing polyorganosiloxane in at least a part of the surface highly hydrophilic over a long period of time.

The polyorganosiloxane is not particularly limited. Specific examples of polyorganosiloxane include polydimethylsiloxane, polymethylethylsiloxane, polymethylphenylsiloxane, polymethylpropylsiloxane, polydiphenylsiloxane, and polymethylbutylsiloxane.
Among these, polydimethylsiloxane is preferable because it is easily available.

Hereinafter, the components contained in the first treatment liquid will be described.

((A) resin)
The resin (A) has a functional group I which is a hydroxyl group and / or a cyano group. Further, the resin (A) has a functional group II which is a hydrophilic group other than the functional group I. The hydrophilic treatment can be performed by using a treatment liquid containing the resin (A) having a hydrophilic group.
The hydrophilic group is not particularly limited as long as it is a functional group conventionally recognized as a hydrophilic group by those skilled in the art, and can be appropriately selected from among them.

The type of the resin (A) is not particularly limited as long as the resin (A) has a predetermined functional group and is soluble in the solvent (B). Examples of the resin (A) include (meth) acrylic resin, novolak resin, polyester resin, polyamide resin, polyimide resin, polyamideimide resin, silicone resin and the like. Among these resins, (meth) acrylic resin is preferable because it is easy to introduce a functional group and adjust the content ratio of a unit having a functional group.

Specific examples of the hydrophilic group include a polyoxyalkylene group (for example, a polyoxyethylene group, a polyoxypropylene group, a polyoxyalkylene group in which an oxyethylene group and an oxypropylene group are blocked or randomly bonded), an amino group, and a carboxy group. Examples include groups, hydroxyl groups and sulfonic acid groups. Further, an organic group containing these groups is also preferable as a hydrophilic group.

Further, a cationic group composed of an anion portion and a cation portion bonded to the resin (A) is also preferable as the hydrophilic group. Examples of the cation portion constituting the cationic group include a nitrogen-containing cation portion, a sulfur-containing cation portion, an iodine-containing cation portion, and a phosphorus-containing cation portion.

The anion constituting the anion portion is not particularly limited. The valence of the anion is not particularly limited, and a monovalent anion or a divalent anion is preferable, and a monovalent anion is more preferable.
Preferable examples of the monovalent anion as the anion portion include halide ions, hydroxide ions, nitrate ions, organic acid ions derived from various organic carboxylic acids and organic sulfonic acids, and the like. Among these, halide ions are preferable, chloride ions, bromide ions, iodide ions, and fluoride ions are more preferable, chloride ions and bromide ions are even more preferable, and chloride ions are particularly preferable.

Preferred examples of the cationic group include a group containing a quaternary ammonium base, a group containing a salt of a nitrogen-containing aromatic heterocyclic group, a group containing a sulfonium base, a group containing an iodonium base, a group containing a phosphonium base and the like. Be done.
Among these cationic groups, a group containing a quaternary ammonium base is preferable because it can be easily introduced into the resin (A) and has a high hydrophilicity effect.

The quaternary ammonium base as a cationic group includes the following formula (AI):
−R ^4a −N ⁺ R ^1a R ^2a R ^3a・ X ⁻・ ・ ・ (AI)
(In the formula (AI), R ^1a , R ^2a , and R ^3a are alkyl groups having 1 to 4 carbon atoms independently bonded to N ⁺ , respectively, and R ^1a , R ^2a , and R ^3a. Two of them may be bonded to each other to form a ring, R ^4a is an alkylene group having 1 to 4 carbon atoms, and X ⁻ is a monovalent anion.)
The group represented by is preferable.

The alkyl groups having 1 or more and 4 or less carbon atoms as R ^1a , R ^2a , and R ^3a may be linear or branched chain, and are preferably linear. Preferable specific examples of R ^1a , R ^2a , and R ^3a include methyl group, ethyl group, n-propyl group, and n-butyl group.

The alkylene group having 1 or more and 4 or less carbon atoms as R ^4a may be linear or branched chain, and is preferably linear. Preferable specific examples of ^R4a include a methylene group, an ethane-1,2-diyl group, a propane-1,3-diyl group, and a butane-1,4-diyl group.

Preferable examples of X ⁻ are the same as the preferred examples of anions constituting the anion portion described above.

When the resin (A) has an anionic group such as a carboxy group or a sulfonic acid group as a hydrophilic group, the ratio of the structural unit having an anionic group to all the structural units of the resin (A) is 5 mol. % Or less.

When the resin (A) has a hydrophilic group containing a hydroxyl group and / or a cyano group as the functional group II, the hydroxyl group and / or the cyano group contained in the hydrophilic group also serves as a functional group I. Fulfill.
Therefore, when the resin (A) has a hydrophilic group containing a hydroxyl group and / or a cyano group as the functional group II, the resin (A) does not have to have the functional group I.
The hydrophilic group containing a hydroxyl group includes the hydroxyl group itself.

In that the treatment liquid has an excellent hydrophilic effect, the hydrophilic group includes the following formula (A1):
-NH-R ¹ ... (A1)
(In the formula (A1), R ¹ is an alkyl group having 1 or more and 4 or less carbon atoms substituted with one or more groups selected from the group consisting of an amino group, a sulfonic acid group, and a hydroxyl group, and the above-mentioned formula ( It is a quaternary ammonium base represented by AI) or a hydrogen atom.)
The group represented by is preferable.

Specific examples of the hydrophilic group represented by the formula (A1) include an amino group and a group having R ¹ represented by the following formula.

Among the specific examples of the hydrophilic group represented by the above formula (A1), a more preferable group includes a group having R ¹ represented by the following formula.

Among the specific examples of the hydrophilic group represented by the above formula (A1), a particularly preferable group includes a group having R ¹ represented by the following formula.

The resin (A) is preferably a polymer of a monomer having an unsaturated bond because it is easy to introduce various functional groups and it is easy to adjust the amount of functional groups. Such a polymer may be a homopolymer or a copolymer.

In this case, the functional group I contained in the resin (A) is the following formula (A2):
CH ₂ = CR ^2- (R ³ ) _a- CO-R ⁴ ... (A2)
(In the formula (A2), R ² is a hydrogen atom or a methyl group, R ³ is a divalent hydrocarbon group, a is 0 or 1, and R ⁴ is -OH, -O-R ^5. , Or -NH-R ⁵ , where R ⁵ is a hydrocarbon group substituted with a hydroxyl group and / or a cyano group.)
It is preferably a group derived from the monomer represented by.

In the above formula (A2), R ³ is a divalent hydrocarbon group. The number of carbon atoms of the divalent hydrocarbon group is not particularly limited as long as the object of the present invention is not impaired. (A) from that resin to obtain and of ease of preparation, the number of carbon atoms of the divalent hydrocarbon group as R ³ is preferably 1 to 20, more preferably 1 to 12, 1 to 10 Is particularly preferable, and 1 or more and 6 or less are most preferable.

The divalent hydrocarbon group as R ³ may be an aliphatic group, an aromatic group, or a hydrocarbon group containing an aliphatic portion and an aromatic portion. When the divalent hydrocarbon group is an aliphatic group, the aliphatic group may be a saturated aliphatic group or an unsaturated aliphatic group. Further, the structure of the aliphatic group may be linear, branched, cyclic, or a combination of these structures.

Suitable specific examples of R ³ include methylene group, ethane-1,2-diyl group, ethane-1,1-diyl group, propane-1,3-diyl group, propane-1,1-diyl group and propane. -2,2-diyl group, n-butane-1,4-diyl group, n-pentane-1,5-diyl group, n-hexane-1,6-diyl group, n-heptan-1,7-diyl group Group, n-octane-1,8-diyl group, n-nonan-1,9-diyl group, n-decane-1,10-diyl group, o-phenylene group, m-phenylene group, p-phenylene group, Examples thereof include naphthalene-2,6-diyl group, naphthalene-2,7-diyl group, naphthalene-1,4-diyl group, biphenyl-4,4'-diyl group and the like.

R ⁴ is -OH, -OR ⁵ or -NH-R ⁵ , and R ⁵ is a hydrocarbon group substituted with a hydroxyl group and / or a cyano group.
Hydrocarbon group constituting the main skeleton of group R ⁵ is a linear, branched, or may be a cyclic aliphatic group may be an aromatic hydrocarbon group.
The number of carbon atoms of the linear, branched, or cyclic aliphatic group is preferably 1 or more and 20 or less, and more preferably 1 or more and 12 or less.
Preferable examples of linear or branched aliphatic groups are methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and tert-butyl group. , N-Pentyl group, Isopentyl group, Neopentyl group, sec-Pentyl group, tert-Pentyl group, n-Hexyl group, n-Heptyl group, n-octyl group, n-nonyl group, n-decyl group and the like. ..
Preferable examples of the cyclic aliphatic group include cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group, and adamantan, norbornan, isobornane, tricyclodecane, Examples thereof include a group obtained by removing one hydrogen atom from a polycycloalkane such as tetracyclododecane, and a group obtained by removing one hydrogen atom from a C1-C4 alkyl substituent of these polycycloalkanes.
Preferable examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthranyl group, a phenanthrenyl group, a biphenylyl group and the like. The aromatic hydrocarbon group may be substituted with a C1-C4 alkyl group such as a methyl group or an ethyl group.

Particularly preferable specific examples of the unit derived from the monomer represented by the formula (A2) include the units a2-1 to a2-8 below. Among the units a2-1 to a2-8 below, the unit a2-1 to a2-3 is more preferable.

Further, the functional group II, which is a hydrophilic group in the resin (A), has the following formula (A3):
CH ₂ = CR ^2- CO-NH-R ¹ ... (A3)
(In the formula (A3), R ¹ is an alkyl group having 1 or more and 4 or less carbon atoms substituted with one or more groups selected from the group consisting of an amino group, a sulfonic acid group, and a hydroxyl group, as described above. It is a quaternary ammonium base or a hydrogen atom represented by AI), and R ² is a hydrogen atom or a methyl group.)
It is preferably derived from the monomer represented by.

In the formula (A3), R ¹ is as described above. As R ¹ , a quaternary ammonium base represented by the above formula (AI) is preferable.

That is, the resin (A) is a unit derived from the monomer represented by the above formula (A3) as the following formula (A4):
_{^{CH 2 = CR 2 -CO-NH}} -R 4a -N + R 1a R 2a R 3a · X - ··· (A4)
(In the formula (A5), R ² is a hydrogen atom or a methyl group, and R ^1a , R ^2a , R ^3a , R ^4a , and X ⁻ are the same as those in the above formula (AI).)
It is preferable to have a structural unit derived from the monomer represented by.

Particularly preferable specific examples of the unit having a hydrophilic group derived from the monomer represented by the formula (A3) include the units a3-1 to a3-5 below.

When the resin (A) is a polymer of a monomer having an unsaturated bond, the polymer is derived from the monomer represented by the above formula (A2) as long as the object of the present invention is not impaired. It may contain other structural units other than the unit to be used and the unit derived from the monomer represented by the formula (A3).

Other constituent units include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, -n-propyl (meth) acrylate, -n-butyl (meth) acrylate, and the like. Isobutyl (meth) acrylate, -tert-butyl (meth) acrylate, -n-pentyl (meth) acrylate, isopentyl (meth) acrylate, phenyl (meth) acrylate, N-methyl (meth) acrylamide, N -Ethyl (meth) acrylamide, Nn-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nn-butyl (meth) acrylamide, Nn-pentyl (meth) acrylamide, N-isopentyl (meth) ) Acrylamide, N-phenyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-di-n-propyl (meth) acrylamide, N, N-di -N-butyl (meth) acrylamide, N, N-di-n-pentyl (meth) acrylamide, styrene, α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, And structural units derived from monomers such as chlorostyrene.

When the resin (A) is a polymer of a monomer having an unsaturated bond, the ratio of the structural units derived from the monomer represented by the formula (A2) in all the structural units contained in the polymer is , 0.1 mol% or more and 50 mol% or less is preferable, 1 mol% or more and 20 mol% or less is more preferable, and 1 mol% or more and 15 mol% or less is particularly preferable.

When the resin (A) is a polymer of a monomer having an unsaturated bond, the molar ratio of the structural unit derived from the monomer represented by (A3) in all the structural units contained in the polymer is , 50 mol% or more and 99.9 mol% or less is preferable, 60 mol% or more and 99 mol% or less is more preferable, and 70 mol% or more and 99 mol% or less is particularly preferable.
However, when the structural unit derived from the monomer represented by the formula (A3) contains a hydroxyl group and / or a cyano group, the single amount represented by the formula (A3) in all the structural units contained in the polymer. The proportion of structural units derived from the body may be 100%.

The weight average molecular weight of the resin (A) is preferably 100,000 or more. When the (A) resin having such a molecular weight is used, the (A) resin is the first member 10 and / or the first member 10 and / or the first member 10 and / or the second due to the reaction or interaction between the functional group I and the surface of the untreated body during the treatment with the treatment liquid. 2 Easy to bond or adhere to member 11.
The weight average molecular weight of the resin (A) is preferably 200,000 or more, more preferably 300,000 or more, from the viewpoint of good surface treatment effect. As long as the resin (A) is soluble in the solvent (B) described later, the weight average molecular weight of the resin (A) may be 1,000,000 or more.
The upper limit of the weight average molecular weight of the resin (A) is not particularly limited as long as the resin (A) is soluble in the solvent (B). The weight average molecular weight of the resin (A) may be, for example, 2.5 million or less, or 4 million or less.

The amount of the resin (A) contained in the treatment liquid is not particularly limited as long as it does not impair the object of the present invention, and is appropriately determined in consideration of the coatability of the treatment liquid and the like. Typically, the amount of the (A) resin in the treatment liquid is preferably the amount having the following relationship between the amount of the (A) resin in the treatment liquid and the amount of the solvent (B) described later. ..
When the mass of the resin (A) in the treatment liquid is 100 parts by mass, the amount of the solvent (B) described later is preferably 100 parts by mass or more and 10,000 parts by mass or less, and 500 parts by mass or more and 8000 parts by mass or less. It is more preferable that the amount is 1000 parts by mass or more and 6000 parts by mass or less.

((B) Solvent)
The solvent (B) is not particularly limited as long as it is a solvent in which the resin (A) is soluble. If a predetermined amount of the resin (A) is dissolved in the treatment liquid, the treatment liquid may contain the resin (A) in an undissolved state and the solvent (B). The resin (A) is preferably completely dissolved in the treatment liquid.
When the treatment liquid contains an insoluble matter, the insoluble matter may adhere to the surface of the first member 10 and / or the second member 11 when the hydrophilic coating 12 is formed. In this case, the surface of the first member 10 and / or the second member 11 is rinsed by a method as described later to remove insoluble matter adhering to the surface of the first member 10 and / or the second member 11. be able to.

The solvent (B) may be water, an organic solvent, or an aqueous solution of an organic solvent.

(B) Specific examples of the organic solvent used as the solvent include
Sulfoxides such as dimethyl sulfoxide;
Sulfones such as dimethyl sulfone, diethyl sulfone, bis (2-hydroxyethyl) sulfone, tetramethylene sulfone;
Amides such as N, N-dimethylformamide, N-methylformamide, N, N-dimethylacetamide, N-methylacetamide, N, N-diethylacetamide;
Lactams such as N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-hydroxymethyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone;
Imidazoridinones such as 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, 1,3-diisopropyl-2-imidazolidinone;
Dialkyl glycol ethers such as dimethyl glycol, dimethyl diglycol, dimethyl triglycol, methyl ethyl diglycol, diethyl glycol, triethylene glycol butyl methyl ether;
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n- Butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, di (Poly) alkylene glycol monoalkyl ethers such as propylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether;
(Poly) alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate;
Other ethers such as dimethyl ether, diethyl ether, methyl ethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diisoamyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;
Lactic acid alkyl esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid Methyl, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, acetic acid Ethyl, acetic acid-n-propyl, acetate-i-propyl, acetate-n-butyl, acetate-i-butyl, formate-n-pentyl, acetate-i-pentyl, propionate-n-butyl, ethyl butyrate, butyric acid Other esters such as -n-propyl, -i-propyl butyrate, -n-butyl butyrate, methyl pyruvate, ethyl pyruvate, -n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate, etc. Kind;
Lactones such as β-propyrolactone, γ-butyrolactone, and δ-pentilolactone;
n-hexane, n-heptane, n-octane, n-nonane, methyloctane, n-decane, n-undecane, n-dodecane, 2,2,4,6,6-pentamethylheptan, 2,2,4 , 4,6,8,8-Heptamethylnonane, cyclohexane, methylcyclohexane and other linear, branched or cyclic aliphatic hydrocarbons;
Aromatic hydrocarbons such as benzene, toluene, xylene, 1,3,5-trimethylbenzene, naphthalene;
Examples thereof include p-menthane, diphenylmenthane, limonene, terpinene, bornane, norbornane, terpenes such as pinan; and the like.

When the solvent (B) is a mixed solvent of water and an organic solvent, the content of the organic solvent in the solvent (B) is preferably 10% by mass or more, more preferably 20% by mass or more.

(Other ingredients)
The treatment liquid may contain various components in addition to the above-mentioned (A) resin and (B) solvent as long as the object of the present invention is not impaired. Examples of other components include pH adjusters, colorants, surfactants, defoamers, viscosity adjusters and the like.

The pH adjusting agent is not particularly limited, and various acids or bases can be used. Since the effect of hydrophilization is good, the pH of the treatment liquid is preferably adjusted to 5 or more and 14 or less, more preferably 5 or more and 12 or less, and adjusted to 5 or more and 10 or less. Is particularly preferable.

(Preparation method of treatment liquid)
The method for preparing the treatment liquid is not particularly limited. The treatment liquid is typically prepared by uniformly mixing a predetermined amount of the resin (A), the solvent (B), and if necessary, other components.

[Second treatment liquid]
Specific examples of a particularly preferable treatment liquid other than the first treatment liquid include the “second treatment liquid” described below.
The second treatment liquid contains (A) resin and (B) solvent.
(A) The ratio of structural units having anionic groups to all structural units of the resin is 5 mol% or less.
(A) When the resin has a functional group I which is a hydroxyl group and / or a cyano group and a functional group II which is a hydrophilic group, except that the functional group II contains a hydroxyl group and / or a cyano group. The resin (A) does not have to have the functional group I.
The resin (A) has a cationic group consisting of an anion portion and a cation portion bonded to the resin (A).
The pH of the second treatment liquid is 5 or more and 14 or less.

The second treatment liquid is the same as the first treatment liquid except that it is essential that the pH is 5 or more and 14 or less. The pH adjustment method is also as described for the first treatment liquid.

The second treatment liquid is preferably used for hydrophilization of various materials, but like the first treatment liquid, it is particularly preferably used for hydrophilization of a member containing polyorganosiloxane in at least a part of the surface.

A hydrophilic film is formed on the surface of the member by using the treatment liquid described above.

<Irradiation process>
As described above, in the irradiation step, in the member provided with the hydrophilic coating, only the joint surface of the hydrophilic coating is selectively irradiated with ultraviolet rays or plasma derived from an oxygen-containing gas. Further, for the member not provided with the hydrophilized coating, at least the joint surface is irradiated with ultraviolet rays or plasma derived from an oxygen-containing gas.

When irradiating with ultraviolet rays, the wavelength of ultraviolet rays and the amount of exposure are not particularly limited as long as the object of the present invention is not impaired. The wavelength of ultraviolet rays is preferably 254 nm or less, and more preferably 172 nm or less, from the viewpoint that the removal of the hydrophilized coating and the activity of the surface of the member by irradiation with ultraviolet rays or plasma can easily proceed at the same time. From the same viewpoint, the exposure amount is preferably 400 mJ / cm ² or more 5000 mJ / cm ² or less, 500 mJ / cm ² or more 2000 mJ / cm ² or less being more preferred.

When performing plasma irradiation, examples of the oxygen-containing gas include oxygen gas, air, and ozone. Further, a gas obtained by mixing oxygen gas, air, or ozone with an inert gas such as nitrogen, helium, or argon can also be used as the oxygen-containing gas.

As described above, the hydrophilic film is removed by irradiating the joint surface, which is the region to be pressure-bonded, in the surface on which the hydrophilic film is formed, with ultraviolet rays or plasma derived from an oxygen-containing gas. At the same time, the surface of the joint surface is activated so that it can be crimped.

<Crimping process>
In the crimping step, an external force is applied to two or more members arranged at predetermined positions so that the joint surfaces of the two or more members treated by ultraviolet rays or plasma face each other, and the joint surfaces are crimped to each other. ..

The load applied to the two or more members at the time of crimping is not particularly limited as long as the members are not destroyed and the two or more members are satisfactorily crimped. The range of the load is, for example, preferably 0.05 kgf or more and 5 kgf or less, more preferably 0.1 kgf or more and 3 kgf or less, and further preferably 0.2 kgf or more and 2 kgf or less.

The time for applying the load is not particularly limited, and for example, 5 seconds or more is preferable, 10 seconds or more is more preferable, and 30 seconds or more is particularly preferable. The upper limit of the time for applying the load is not particularly limited, and is appropriately determined in consideration of the productivity of the flow path device. The time for applying the load may be, for example, 60 hours or less, 10 hours or less, 1 hour or less, or 10 minutes or less.

After applying the load, it is also preferable to allow the flow path device formed by the crimping to stand still, if necessary, in order to make the crimping more reliable.
The standing time is not particularly limited, and is preferably 10 minutes or more, more preferably 20 minutes or more, and even more preferably 30 minutes or more. The upper limit of the standing time is not particularly limited, and is appropriately determined in consideration of the productivity of the flow path device. The standing time may be, for example, 100 hours or less, 50 hours or less, 10 hours or less, 5 hours or less, or 1 hour or less.

According to the method through the film forming step, the irradiation step, and the crimping step described above, a flow path device capable of maintaining the hydrophilicity of the surface of the flow path for a long period of time can be easily manufactured.

As the method explained above,
It is a method of using two members, a first member and a second member, as two or more members.
The first member is a plate-shaped member having a groove corresponding to the flow path.
The second member is a plate-shaped member having a non-stepped surface composed of a flow path surface and a joint surface as a surface on the side to be joined to the first member.
A method is preferred in which the flow path surface of the second member closes the opening of the groove provided in the first member to form the flow path.
In such a method, since the surface of the second member on the side to be joined to the first member is the inner surface of the step, the two members are used when the first member and the second member are crimped. It is possible to easily manufacture a flow path device having a desired shape without performing precise positioning.

Hereinafter, typical examples of the above manufacturing method will be described in FIG. 1 (FIG. 1 (a1), FIG. 1 (a2), FIG. 1 (b1), FIG. 1 (b2), FIG. 1 (c1), FIG. 1 (c2). , And FIG. 1 (d)). The number and shape of the members constituting the flow path device, the shape of the flow path device, and the like are not limited to the modes shown in FIG.

(Film formation process)
In the film forming step, first, two or more members are prepared as the members constituting the flow path device 1. The shape and size of the two or more members are not particularly limited as long as the flow path device can be manufactured by combining all the members.
FIG. 1 describes a method of manufacturing a flow path device 1 by using two members including a first member 10 having a recess corresponding to a flow path and a flat plate-shaped second member 11. FIG. 1 (a1) shows the first member 10, and FIG. 1 (a2) shows the second member 11.

The materials of the first member 10 and the second member 11 are as described above.

In the film forming step, at least one of the first member 10 and the second member 11 uses a treatment liquid containing a hydrophilizing agent to coat the surface of the member to be joined to the other members of the member. To form.

In FIGS. 1 (b1) and 1 (b2), the hydrophilic coating 12 is formed on both the surface of the first member 10 on the bonded side and the surface of the second member 11 on the bonded side. There is.
The hydrophilized coating 12 may be formed on a surface other than the surface to be joined. However, since the process of forming the hydrophilic coating 12 becomes complicated, it is preferable that the hydrophilic coating 12 is formed only on the surface of the member to be joined.

The thickness of the hydrophilized coating 12 is not particularly limited as long as it does not impair the object of the present invention. The preferred thickness range of the hydrophilized coating 12 is as described above.

(Irradiation process)
In the irradiation step, as shown in FIGS. 1 (c1) and 1 (c2), the hydrophilic coating 12 is joined in the member (first member 10 and / or second member 11) provided with the hydrophilic coating 12. Only the surface is selectively irradiated with ultraviolet rays or plasma derived from an oxygen-containing gas.
In FIG. 1, both the first member 10 and the second member 11 are provided with the hydrophilic coating 12, but the member without the hydrophilic coating 12 is exposed to ultraviolet rays or oxygen-containing gas at least with respect to the joint surface. Irradiate the resulting plasma.

The conditions for irradiating plasma derived from ultraviolet rays or oxygen-containing gas are as described above.

(Crimping process)
In the crimping step, both the first member 10 and the second member 11 treated by ultraviolet rays or plasma are predetermined so that their joint surfaces face each other as shown in FIG. 1 (d). Place it in the correct position. Then, an external force is applied to the first member 10 and the second member 11 arranged at predetermined positions to crimp the joint surfaces to each other.

The conditions for crimping are as described above.

According to the method described above, a channel device capable of maintaining the hydrophilicity of the surface of the channel for a long period of time can be easily manufactured.

Hereinafter, the present invention will be described in more detail with reference to Examples. The scope of the present invention is not limited to these examples.

[Example 1]
In Example 1, by crimping two flat polydimethylsiloxane sheets by the above-mentioned method, the effect of hydrophilization by the hydrophilic film and the effect of easy and strong crimping were simulated.

After applying Cylgard 184 (manufactured by Shin-Etsu Chemical Co., Ltd.) on a silicon wafer, the coating film was heated at 150 ° C. for 30 minutes to prepare two polydimethylsiloxane sheets.
One surface of the obtained polydimethylsiloxane sheet was irradiated with ultraviolet rays having a wavelength of 172 nm by a vacuum ultraviolet irradiation device (EX-400, manufactured by Hamamatsu Photonics Co., Ltd.) at an exposure amount of 364 mJ / cm ² , and a hydrophilic film was formed. Pretreatment for formation was performed.
Next, a hydrophilic film was formed using the following aqueous solution of Resin 1 having a concentration of 1% by mass as a treatment solution. In the following formula, n, m, and l described in the lower right of the parentheses represent the mol% of each structural unit in all the structural units in the resin. n is 70 mol% or more and 90 mol% or less, m is 5 mol% or more and 20 mol% or less, and l is 5 mol% or more and 10 mol% or less.

More specifically, the above treatment liquid is dropped on the surface of the polydimethylsiloxane sheet that has been irradiated with ultraviolet rays with a dropper and spread, and then the coating film is dried under the condition of 80 ° C. for 5 minutes, and then coated. The surface of the membrane was rinsed with running water to form a hydrophilic film. The film thickness measured by ellipsometry of the formed hydrophilic film was 2 nm.

The contact angle of water on the surface containing the hydrophilic film was measured 1 hour, 3 hours, 12 hours, and 1 week after the formation of the hydrophilic film, and the change over time of the hydrophilic effect was evaluated.
The contact angle of water is measured by dropping a pure water droplet (2.0 μL) on the surface of a substrate surface-treated using Dropmaster700 (manufactured by Kyowa Interface Science Co., Ltd.) and measuring it as the contact angle 10 seconds after the drop. did.
As a result of the above evaluation, the contact angle of water on the surface of the polydimethylsiloxane sheet having the hydrophilized coating was less than 10 ° at any of the measurement times after 1 hour, 3 hours, and 12 hours. It was stable. Moreover, even in the measurement after one week, the contact angle of water was a low value of 20 ° C. or less.
The contact angle of water on the surface of the polydimethylsiloxane sheet without the hydrophilic film is 110 °.

Of the surfaces on which the hydrophilic coatings of the two polydimethylsiloxane sheets having the above hydrophilic coatings are formed, only the region to be bonded to the other sheet is a vacuum ultraviolet irradiation device (EX-400). , Hamamatsu Photonics Co., Ltd.) irradiated ultraviolet rays having a wavelength of 171 nm at an exposure amount of 728 mJ / cm ² to activate the surface.
After arranging the two polydimethylsiloxane sheets so that the surfaces activated by the ultraviolet irradiation face each other, the two polydimethylsiloxane sheets were pressure-bonded under a load of 1 kgf for 1 minute. The two crimped polydimethylsiloxane sheets were allowed to stand at room temperature for 48 hours, and then the crimped state of the two sheets was confirmed, but they were firmly crimped and were not peeled off.

[Example 2]
As a pretreatment for forming a hydrophilic film, instead of irradiating ultraviolet rays with a vacuum ultraviolet irradiation device, an oxygen plasma device (TCA-3822, manufactured by Tokyo Ohka Kogyo Co., Ltd.) is used, 100% oxygen, RF Power: 50W. Except for the irradiation of oxygen plasma under the condition of 10 seconds, the formation of a hydrophilic film, the irradiation of ultraviolet rays on the surface on which the hydrophilic film was formed, and two polydimethyls were performed as in Example 1. The siloxane sheet was crimped. The two crimped polydimethylsiloxane sheets were allowed to stand at room temperature for 6 hours, and then the crimped state of the two sheets was confirmed, but they were firmly crimped and were not peeled off.

[Example 3]
Hydrophilization in the same manner as in Example 2 except that the exposure amount during ultraviolet irradiation for surface activation on the surface on which the hydrophilic film was formed was changed from 728 mJ / cm ² to 1092 mJ / cm ² . The film was formed, the surface on which the hydrophilic film was formed was irradiated with ultraviolet rays, and the two polydimethylsiloxane sheets were pressure-bonded. The two crimped polydimethylsiloxane sheets were allowed to stand at room temperature for 6 hours, and then the crimped state of the two sheets was confirmed, but they were firmly crimped and were not peeled off.

[Example 4]
Hydrophilization in the same manner as in Example 2 except that the exposure amount during ultraviolet irradiation for surface activation on the surface on which the hydrophilic film was formed was changed from 728 mJ / cm ² to 546 mJ / cm ² . The film was formed, the surface on which the hydrophilic film was formed was irradiated with ultraviolet rays, and the two polydimethylsiloxane sheets were pressure-bonded. The two crimped polydimethylsiloxane sheets were allowed to stand at room temperature for 6 hours, and then the crimped state of the two sheets was confirmed, but they were firmly crimped and were not peeled off.

[Comparative Example 1]
The formation of the hydrophilic film and the pressure bonding of the two polydimethylsiloxane sheets were carried out in the same manner as in Example 2, except that the surface on which the hydrophilic film was formed was not irradiated with ultraviolet rays for surface activation. Was done. After allowing the two crimped polydimethylsiloxane sheets to stand at room temperature for 13 hours, the crimped state of the two sheets was confirmed, but the two polydimethylsiloxane sheets were easily peeled off from the crimped interface. did.

1 Flow path device 10 1st member 11 2nd member 12 Hydrophilized coating

Claims (10)

A method for manufacturing a flow path device having a flow path for flowing a liquid inside.
Two or more members are prepared as members constituting the flow path device, and at least one of the members uses a treatment liquid containing a hydrophilic agent to form a surface on the side to be joined to the other members of the member. A film forming process that forms a hydrophilic film to be coated,
In the member provided with the hydrophilized coating, only the joint surface of the hydrophilized coating is selectively irradiated with plasma derived from ultraviolet rays or an oxygen-containing gas, and the member not provided with the hydrophilic coating is provided. An irradiation step of irradiating at least the joint surface with plasma derived from ultraviolet rays or an oxygen-containing gas.
An external force is applied to the two or more members arranged at predetermined positions so that the joint surfaces of the two or more members treated by the ultraviolet rays or the plasma face each other, and the joint surfaces are brought together. Crimping process and crimping process
Manufacturing method, including. The method for manufacturing a flow path device according to claim 1, wherein the portion of the hydrophilic coating that is not irradiated with plasma derived from ultraviolet rays or oxygen-containing gas is the flow path surface of the flow path device. The method for manufacturing a flow path device according to claim 1 or 2, wherein the hydrophilized coating is formed on all of the two or more members. Claim that before forming the hydrophilic film, a treatment of irradiating the surface on which the hydrophilic film is formed with plasma derived from ultraviolet rays or an oxygen-containing gas or a treatment of contacting the surface with an oxidizing agent is performed. The method for manufacturing a flow path device according to any one of 1 to 3. The method for producing a flow path device according to claim 4, wherein the oxidizing agent is at least one selected from the group consisting of sulfuric acid, nitric acid, chromic acid, permanganic acid, persulfuric acid, and mixed acid. The method for manufacturing a flow path device according to any one of claims 1 to 5, wherein the hydrophilic agent is an organic compound and the film thickness of the hydrophilic film is 100 nm or less. The method for manufacturing a flow path device according to any one of claims 1 to 6, wherein in the irradiation step, the ultraviolet rays are irradiated and the wavelength of the ultraviolet rays is 254 nm or less. The method for manufacturing a flow path device according to claim 7, wherein the wavelength of the ultraviolet rays is 172 nm or less. One type selected from the group consisting of silicon, glass, silicone resin, cyclic olefin polymer, cyclic olefin copolymer, acrylic resin, polyester resin, and polycarbonate resin as the material of the surface of the member to be joined to other members. The method for manufacturing a flow path device according to any one of claims 1 to 6, which is the above. The two or more members are composed of two members, a first member and a second member.
The first member is a plate-shaped member having a groove corresponding to the flow path.
The second member is a plate-shaped member having a non-stepped surface composed of a flow path surface and a joint surface as a surface on the side to be joined to the first member.
The flow path device according to any one of claims 1 to 9, wherein the flow path surface of the second member closes the opening of the groove provided in the first member to form the flow path. Manufacturing method.

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